Department of Chemistry

Physical Chemistry Lab I

CHEM 355

Fall 2020

Partial Molal Volumes

Student name:

Lulua Al Janahi 201600103

Date of experiment: 21/9/2020

Section: 52

Instructor: Joanna Pajak

Introduction:
Good knowledge of the thermophysical properties of electrolyte solutions

is essential to the understanding of natural processes and the design of a

wide range of industrial processes. In this experiment, therefore, we

analyze the density and corresponding volumetric properties in electrolyte

solutions where the electrolyte is NaCl and the solvent is water.

The total volume of solution containing 1 kg (55.51 moles) of water and

m moles of solute shall be determined by

V =n1 V 1 +n 2 V 2=55.51 V 1+ mV 2

where the subscripts 1 and 2 refer to solvent and solute, respectively. Let

0 18.016 g mol−1 3
be the molar volume of pure water(¿ =18.069 cm mol ).
−1
V1 −3
0.997004 g cm

Then we describe the measurable molar volume of the solute by the

equation:

V =n1 V 10 +n 2 φ v =55.51V 10 +mφ

which can be rearranged to give:

1 1
φ= ( V −n1 V 10)= (V −55.51V 10 )
n2 m

Now

1000+m M 2
V=
d

And

2
 1000
n1 V 1 0 =
d0

where d is the density of the solution and d 0 is the density of pure solvent,

both in units of g . cm−1, m is the molality in mol . kg−1and M 2is the solute

molecular weight in grams per mole. By substituting we get:

1 1000 d−d 0
φ= (M 2− )
d m d0

Now by the definition of partial molar volumes and by use of the above

equations:

V 2=¿

Also,

V −n2 V 2 1 ∂φ m2 ∂ φ
V 1=
n1
=
n1(n1 V 10 −n22
)
∂ n2
=V 10−
55.51 ∂ m

We may continue by plotting φ vs. m, drawing a smooth curve through

the points, and establishing tangents to the curve at the desired

concentrations to quantify the slopes. However, in the case of basic

electrolyte solutions, it has been observed that certain apparent molar

quantities, such as φ, differ linearly with √ m or even to mild

concentrations. This action is consistent with the prediction of the Debye-

Huckel theory for dilute solutions. Since :

∂φ ∂ φ ∂√ m 1 ∂φ
= =
∂m ∂√m ∂m 2√ m ∂√ m

We obtain:

3
V 2=φ+
m dφ
=φ+
√ m dφ =φ0 + 3 √ m dφ
2 √m d √m 2 d √m 2 d √m

m √ m dφ
V 1=V 10− ( )
55.51 2 d √m

Since φ 0 is the apparent molar volume extrapolated to zero concentration.

Now we can plot φ versus √ mand select the best straight line through the

dφ
dots. Both V 1 and V 2 can be obtained from the slope and the value of
d √m

φ 0.

This experiment aimed to use an accurate density determination to

measure the partial molar volumes of the NaCl in the solution. Partial

molar volume is the contribution of a mixture component to the total

volume of the solution. The mass of both water and NaCl was measured

using an analytical balance. To ensure accurate and precise

measurements, the pycnometers were filled until the capillaries were

filled with a solution and any solution dripped outside was dry.

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Experimental Method:
Equipment and materials :

 25 mL volumetric flasks
 10 mL pipettes
 pycnometer
 3M NaCl solution
 Disstelled water
 Balance

Procedure:

1. From the stock solution of NaCl (3M) prepare 25 mL of the NaCl

solutions of the following molarities: 3.0 M, 1.5M, 0.75M, 0.
375M, 0.1875M.
2. Weight the prepared solutions.

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Results & Calculations:

mass of pycnometer (g)= 17.747 g

mass of pycnometer + water (g) = 27.6502g

mass of water (g) = 27.6502- 17.747= 9.9032g

density of water (g/ml) =0.9978 g/mL

volume of pycnometer (ml) =9.925ml

Volume M mass pycn. +sol. mass sol. (g) density sol.

of 3.0M mol/L (g) (g/ml)
3.0 28.7914 11.0444 1.113
12.0 1.44 28.2044 10.4574 1.054
6.0 0.72 27.9352 10.1882 1.027
3.0 0.36 27.7962 10.0492 1.013
1.5 0.18 27.7219 9.9749 1.005

M mol/L d [g/mL] m √m φ
mol/kg
3 1.113 3.199 1.7885749 20.09
1.44 1.054 1.485 1.2186058 19.47
0.72 1.027 0.731 0.8549854 17.93
0.36 1.013 0.363 0.6024948 16.37
0.18 1.005 0.181 0.4254409 18.49

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 m [mol/kg] V 1 [mL/mol] V 2 [mL/mol]
0 18.069 16.477
0.5 18.062 18.639
1.5 18.035 20.221
2.0 18.017 20.801
2.5 17.996 21.311

𝜙 vs. √m

21

20 f(x) = 2.04 x + 16.48

19

18
φ

17

16

15
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
√m

V 1 vs m

18.08

18.06

18.04

18.02
m

18

17.98

17.96

17.94
0 0.5 1 1.5 2 2.5 3
¯𝑉1

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V 2 vs m

22

21

20

19
m

18

17

16
0 0.5 1 1.5 2 2.5 3

¯𝑉2

Calculations:
g
M 2=58.45
mol
V 10=18.069 cm 3 mol−1
dφ
slope ( )
d √m
=2.0382

φ 0=16.477

Converting molarity(M) to molality(m):

1
m=
d M
( )
M
−( 2 )
1000
1
m= =1.485 m
1.054 58.45
(1.44
−( )
1000
)

Calculate φ:
1 1000 d−d 0
φ= (M 2− )
d m d0
1
φ= ¿
1.054

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Calculate V 1:
m √ m dφ
V 1=V 10− ( )
55.51 2 d √m
1.5
V 1=18.069−
55.51 ( √1.52 2.0382)=18.035 mol
mL

Calculate V 2:
3 m dφ
V 2=φ0 + √
2 d √m
3 1.5 mL
V 2=16.477+ √ 2.0382=20.221
2 mol

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Discussion:

In this experiment, the object was achieved by determining the partial

molar volumes of sodium chloride solution as a function of concentration

from density measurement. We calculated the apparent molar volume (φ)

using the density and at different molality, and the calculation’s results

are shown in the second table. The relationship was found to be linear

with a positive slope between φ and √m as it was shown in the first

graph. As the square root of the molality increases the apparent molal

volume increases. Then we got the slope which is ( ddφ√m ) from the
trendline equation to be 2.0382. Also from the equation, the Y-intercept is

the apparent molal volume at zero concentration (φ 0 ¿ which is 16.477. In

the third table the partial molal volumes V́ 1 andV́ 2(water and NaCl) is

listed at different molality. The second graph showed the relationship

between V́ 1∧the molality (m) which is an inversed relationship, where the V́ 1

increased while the molality (m) decreased. While the third graph showed

the proportional relationship between V́ 2∧the molality (m), when the value

of V́ 2increased, the molality (m) increased.

particularly, when the ideal solution is completely combined so that the

sum of the partial volume is equal to the final volume. However, the ideal

solution is not assured to be fully combined. Partial molar volume is the

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volume expansion or reduction that happens when one mole of

component is added to the solution. The solvent concentration is equal to

the solution density. Partial molar volume is highly affected by the

concentration of the solution. The higher the concentration, the larger is

the partial molar number. Errors in this experiment might be attributed to

defective pycnometers, or not completely wiping the overspill from the

side of the pycnometer.

Reference:
Physical Chemistry Lab I Manual “CHEM 355”

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